Beta-amino ester compounds and uses thereof

ABSTRACT

Hair treatment compositions are disclosed comprising a β-amino ester compound in a cosmetically acceptable vehicle, such as a spray or cream. In embodiments, the compounds include a polybutadiene moiety. Methods of treating hair with the compositions to impart volume, texture and definition are also disclosed.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a divisional of U.S. application Ser. No.12/354,697, filed Jan. 15, 2009, the entire contents of which areincorporated herein by reference.

BACKGROUND OF THE INVENTION Field of the Invention

The invention is directed to compositions and methods for treating hair,and in particular to methods and compositions for imparting thickness,volume, texture and definition, which permit improved styling.

DESCRIPTION OF RELATED ART

Hair treatment products on the market typically use commercial polymersto impart volume, texture, definition and thickness. People with fine orthin hair regularly use “volumizing” products in the form of shampoos,conditioners, styling sprays, creams, gels, or mousses in an effort toincrease the volume and body of their hair. Many of these materials arepolyvinylpyrrolidone/polyvinyl acetate (PVP/VA) combinations. Thesematerials create volume in hair by binding multiple hair fibers togetherin spot-welds, such that a droplet of the product lands on a section ofthe hair thereby linking a hair fiber back on itself and/or linking twoor more fibers, creating stiffer hair, more resistant to, for example,falling flat on the head. This technology suffers from severaldrawbacks, as the visual benefits obtained do not last and the hair isleft feeling stiff or crunchy. Thus, it is desired to identify anddevelop compositions that achieve these results with greater ease ofuse, less heaviness and less feeling of sticky residue, that do notimpart a crunchy or stiff feeling to the hair, and which impart shineand softness to the hair as well as volume and thickness.

Preparation of poly(β-amino esters) from conjugate addition ofbis(secondary amines) or primary amines to a bis(acrylate ester) isdescribed in U.S. Pat. Nos. 6,998,115 and 7,427,394, and relatedapplications, the disclosures of which are incorporated herein byreference in their entirety. Many of the compounds within the scope ofthe disclosure are said to be biodegradable and biocompatible and saidto be useful in a variety of drug delivery systems. However, use incosmetics is not contemplated in these patents.

SUMMARY OF THE INVENTION

Whereas advances in the art typically involve new formulations of knowncompounds, the inventors herein have brought real innovation to thefield of hair treatment at the compound level, developing new molecularentities for use in styling hair. Of particular interest are hairstyling compositions that avoid reliance on conventional high-molecularweight PVP/VA compounds, that provide a lighter, more natural feel,while still providing thickness, texture, volume and definition.

In one aspect, the invention involves the use of the compounds such asare disclosed in U.S. Pat. Nos. 7,427,394 and 6,998,115; U.S. PatentApplication Publication Nos. U.S. 2004/0071654 and U.S. 2005/0265961;and International Application Nos. WO 02/31025; WO 04/106411 and WO07/143659 with a cosmetically acceptable carrier in a composition fortreatment of hair. The disclosure of each of the aforesaid patents andpublished applications is incorporated by reference herein.

Thus, in one aspect, the invention is a hair treatment compositioncomprising a compound according to formula (I) or (I′)in a cosmeticallyacceptable carrier:

In formula (I) and (I′), n is an integer between 1 and 10,000; and Z andZ′, together with the atoms to which they are attached, representacrylate, methacrylate or amino end groups.

The substituent R₂ is the residue of a primary amine starting material,which may be reacted with a diacrylate or dimethacrylate startingmaterial, to form the compound according to formula (I) or (I′), asdescribed in greater detail below. For example, R₂ may be selected fromthe group consisting of alkyl, alkenyl, alkynyl, acyl, alkoxy,alkoxyalkyl, amino, aminoalkyl, aryl, heteroaryl, amido, alkylthioether,carbamoyl, carbonyldioxyl, carboxyl ester, cyclic aliphatic, cyclicheteroaliphatic, aromatic, heteroaromatic and ureido groups, each ofwhich groups may be substituted with at least one substituent selectedfrom the group consisting of alkyl, alkenyl, alkynyl, acyl, alkoxy,alkoxylalkyl, amino, aminoalkyl, aryl, heteroaryl, amido, cyclicaliphatic, heterocyclic aliphatic, halogen, hydroxyl, cyano, carbamoyl,carboxylic acid, carbonyldioxyl, alkylthioether, siloxyl, andthiohydroxyl groups.

A is a carbon chain or a heteroatom-containing carbon chain, optionallysubstituted with at least one substituent selected from the groupconsisting of alkyl, alkenyl, alkynyl, amino, alkylamino, dialkylamino,trialkylamino, aminoalkyl aryl, ureido, heterocyclic, aromaticheterocyclic, cyclic, aromatic cyclic, halogen, hydroxyl, alkoxy, cyano,amido, carbamoyl, carboxylic acid, ester, carbonyl, carbonyldioxyl,alkylthioether, and thiol groups; wherein said substituents may join toform one or more rings.

Alternatively, a bis(amine) is used as a starting material and isreacted with the diacrylate or dimethacrylate starting material so thatthe hair treatment composition comprises a compound according to formula(II) or (II′).

In formula (II) and (II′), A, n, Z and Z′ are as defined for formula(I); R₃ and R₄ are defined as for R₂ in Formula (I); and B and A are,independently, a carbon chain or a heteroatom-containing carbon chain,optionally substituted with at least one substituent selected from thegroup consisting of alkyl, alkenyl, alkynyl, amino, alkylamino,dialkylamino, trialkylamino, aminoalkyl, aryl, ureido, heterocyclic,aromatic heterocyclic, cyclic, aromatic cyclic, halogen, hydroxyl,alkoxy, cyano, amido, carbamoyl, carboxylic acid, ester, carbonyl,carbonyldioxyl, alkylthioether, and thiol groups.

In another aspect of the invention, oligomers are provided which haveβ-amino ester monomer units bonded to blocks of repeating monomer units(such as polybutadiene blocks). In particular, it has now been foundthat compounds having a β-amino ester moiety and a rubber moiety innovel and useful hair treatment compositions avoid the drawbacks of thevolumizing products known in the prior art.

Without wishing to be bound by any particular theory, it is believedthat the β-amino ester compounds disclosed herein bind to the hairfibers to increase inter-fiber friction and produce benefits notdelivered through conventional technology. The inventive compositionincrease friction in hair while allowing hair fibers to remain free tomove, allowing for a more natural feel. In addition, the inventivecompositions afford longer lasting and re-shapeable hair styles. Fibersare free to separate and re-attach at different points, allowing for amore natural feel and movement. These effects are achieved according tothe invention using the compositions and methods described herein. As aresult, the present inventive compositions and methods are believed toavoid making the hair feel stiff or crunchy.

Thus, in this further aspect, the invention is a hair treatmentcomposition comprising a compound according to formula (I) or formula(II) wherein A is a rubber moiety, such as, without limitation, a moietymade up of one or more units of butadiene, isoprene, chloroprene,styrene-butadiene, mixtures thereof, or variations thereof.

In preferred embodiments, a hair treatment composition according to theinvention comprises a compound of formula (III) in a cosmeticallyacceptable carrier:

In the above formula (III), n is an integer between 1 and 10,000; y isan integer between 1 and 10,000; and R₂ is selected from the groupconsisting of alkyl, alkenyl, alkynyl, acyl, alkoxy, alkoxyalkyl, amino,aminoalkyl, aryl, heteroaryl, amido, alkylthioether, carbamoyl,carbonyldioxyl, carboxyl ester, cyclic aliphatic, cyclicheteroaliphatic, aromatic, heteroaromatic and ureido groups, each ofwhich groups may be substituted with at least one substituent selectedfrom the group consisting of alkyl, alkenyl, alkynyl, acyl, alkoxy,alkoxylalkyl, amino, aminoalkyl, aryl, heteroaryl, amido, cyclicaliphatic, heterocyclic aliphatic, halogen, hydroxyl, cyano, carbamoyl,carboxylic acid, carbonyldioxyl, alkylthioether, siloxyl, andthiohydroxyl groups.

Alternatively, a hair treatment composition according to the inventionmay comprise a compound according to formula (IV) in a cosmeticallysuitable carrier, wherein y, n, Z, Z′, B, R₃ and R₄ are all defined asset forth above with respect to formulas (I), (II) and (III):

Methods according to the invention comprise the step of contacting scalphair with the composition containing a compound according to any offormulas (I) through (IV) in a cosmetically acceptable carrier, asdescribed in greater detail in the detailed description that follows.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

The advantages of the compositions and formulations according to theinvention are brought about by incorporating specific β-amino estermoieties and specific linking moieties according to the invention. Insome cases (not to be construed as limiting), the formulations have beenadapted for shaping hair. It has been found that some of thesecompositions afford the user the ability not only to shape the hair, butthe ability to reshape a style after it has been significantly altered(after a night's sleep for example). The methods and specific examplesof reacting diacrylates and amines, and the compounds and functionalresults achieved thereby, are described in greater detail in thefollowing detailed description of the invention.

Definitions

Definitions of specific functional groups and chemical terms aredescribed in more detail below. For purposes of this invention, thechemical elements are identified in accordance with the Periodic Tableof the Elements, CAS version, Handbook of Chemistry and Physics, 75^(th)Ed., and specific functional groups are generally defined as describedtherein. Additionally, general principles of organic chemistry, as wellas specific functional moieties and reactivity, are described in OrganicChemistry, Thomas Sorrell, University Science Books, Sausalito (1999),the entire contents of which are incorporated herein by reference.

Unless expressly stated otherwise, the compounds and groups describedherein may be substituted with any number of substituents or functionalmoieties permitted by the valences of the respective compound or group.In general, the term “substituted” whether preceded by the term“optionally” or not, and substituents contained in formulas of thisinvention, refer to the replacement of hydrogen atoms in a givenstructure with a specified substituent. Unless stated otherwise, whenmore than one position in any given structure may be substituted withmore than one substituent selected from a specified group, thesubstituent may be either the same or different at every position. Asused herein, the term “substituted” is contemplated to include allpermissible substituents of organic compounds. In a broad aspect, thepermissible substituents include acyclic and cyclic, branched andunbranched, carbocyclic and heterocyclic, aromatic and non-aromaticsubstituents of organic compounds. For purposes of this invention,heteroatoms such as nitrogen, oxygen or sulfur, may be bonded tohydrogen atoms or be substituted with any permissible substituents oforganic compounds described herein which satisfy the valencies of theheteroatoms.

Where a carbon atom in a chain may be replaced with a heteroatom, thisis also sometimes referred to as a “substitution.”

The term acyl as used herein refers to a group having the generalformula —C(O)R, where R is alkyl, alkenyl, alkynyl, aryl, carbocylic,heterocyclic, or aromatic heterocyclic. An example of an acyl group isacetyl.

As used herein, an acrylate radical, and/or end group has the structure

A methacrylate radical and/or end group has the structure

The term aliphatic, as used herein, includes both saturated andunsaturated, straight chain (i.e., unbranched), branched, acyclic,cyclic, or polycyclic aliphatic hydrocarbons, which are optionallysubstituted with one or more functional groups. As will be appreciatedby one of ordinary skill in the art, “aliphatic” is intended herein toinclude, but is not limited to, alkyl, alkenyl, alkynyl, cycloalkyl,cycloalkenyl, and cycloalkynyl moieties.

The term alkyl as used herein refers to a saturated, straight- orbranched-chain hydrocarbon radicals derived from a hydrocarboncontaining between one and twenty carbon atoms by removal of a singlehydrogen atom. In some embodiments, the alkyl group contains 1-10 carbonatoms. In another embodiment, the alkyl group contains 1-8 carbon atoms.In still other embodiments, the alkyl group contains 1-6 carbon atoms.In yet another embodiment, the alkyl group contains 1-4 carbons.Examples of alkyl radicals include, but are not limited to, methyl,ethyl, n-propyl, isopropyl, n-butyl, iso-butyl, sec-butyl, sec-pentyl,iso-pentyl, tert-butyl, n-pentyl, neopentyl, n-hexyl, sec-hexyl,n-heptyl, n-octyl, n-decyl, n-undecyl, dodecyl, and the like, which maybear one or more substituents. As used herein, the term “alkyl” includesstraight, branched and cyclic alkyl groups. An analogous conventionapplies to other generic terms such as “alkenyl”, “alkynyl”, and thelike. Furthermore, as used herein, the terms “alkyl”, “alkenyl”,“alkynyl,” and the like, encompass both substituted and unsubstitutedgroups. In certain embodiments, as used herein, “lower alkyl” is used toindicate those alkyl groups (cyclic, acyclic, substituted,unsubstituted, branched or unbranched) having 1-6 carbon atoms.

The term alkoxy as used herein refers to a saturated (i.e., alkyl—O—) orunsaturated (i.e., alkenyl—O— and alkynyl—O—) group attached to theparent molecular moiety through an oxygen atom. In certain embodiments,the alkyl, alkenyl or alkynyl group contains 1-20 aliphatic carbonatoms. In certain other embodiments, the alkyl, alkenyl, and alkynylgroups employed in the alkoxy groups of the invention contain 1-8aliphatic carbon atoms. In still other embodiments, the alkyl groupcontains 1-6 aliphatic carbon atoms. In yet other embodiments, the alkylgroup contains 1-4 aliphatic carbon atoms. Examples include, but are notlimited to, methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, tert-butoxy,i-butoxy, sec-butoxy, neopentoxy, n-hexoxy, and the like.

The term alkenyl denotes a monovalent group derived from a hydrocarbonmoiety having at least one carbon-carbon double bond by the removal of asingle hydrogen atom. In certain embodiments, the alkenyl group employedin the invention contains 1-20 carbon atoms. In some embodiments, thealkenyl group employed in the invention contains 1-10 carbon atoms. Inanother embodiment, the alkenyl group employed contains 1-8 carbonatoms. In still other embodiments, the alkenyl group contains 1-6 carbonatoms. In yet another embodiments, the alkenyl group contains 1-4carbons. Alkenyl groups include, for example, ethenyl, propenyl,butenyl, 1-methyl-2-buten-1-yl, and the like.

The term alkynyl as used herein refers to a monovalent group derivedfrom a hydrocarbon having at least one carbon-carbon triple bond by theremoval of a single hydrogen atom. In certain embodiments, the alkynylgroup employed in the invention contains 1-20 carbon atoms. In someembodiments, the alkynyl group employed in the invention contains 1-10carbon atoms. In another embodiment, the alkynyl group employed contains1-8 carbon atoms. In still other embodiments, the alkynyl group contains1-6 carbon atoms. Representative alkynyl groups include, but are notlimited to, ethynyl, 2-propynyl (propargyl), 1-propynyl, and the like.

The term alkylamino, dialkylamino, and trialkylamino as used hereinrefers to one, two, or three, respectively, alkyl groups, as previouslydefined, attached to the parent molecular moiety through a nitrogenatom. The term alkylamino refers to a group having the structure —NHR′wherein R′ is an alkyl group, as previously defined; and the termdialkylamino refers to a group having the structure —NR′R″, wherein R′and R″ are each independently selected from the group consisting ofalkyl groups. The term trialkylamino refers to a group having thestructure —NR′R″R′″, wherein R′, R″, and R′″ are each independentlyselected from the group consisting of alkyl groups. In certainembodiments, the alkyl group contain 1-20 aliphatic carbon atoms. Incertain other embodiments, the alkyl group contains 1-10 aliphaticcarbon atoms. In yet other embodiments, the alkyl group contains 1-8aliphatic carbon atoms. In still other embodiments, the alkyl groupcontain 1-6 aliphatic carbon atoms. In yet other embodiments, the alkylgroup contain 1-4 aliphatic carbon atoms. Additionally, R′, R″, and/orR′″ taken together may optionally be —(CH₂)_(k)— where k is an integerfrom 2 to 6, to form a ring. Examples include, but are not limited to,methylamino, dimethylamino, ethylamino, diethylamino,diethylaminocarbonyl, methylethylamino, iso-propylamino, piperidino,trimethylamino, and propylamino.

An amino group, as used herein, encompasses alkylamino, dialkylamino andtrialkylamino groups (as defined above), and aminoalkyl likewiseincludes —RNH₂, —RNHR', —RNR′R″ and —RNR′R″R′″. In preferred embodimentsaccording to the invention, a substituted aminoalkyl group, such as adiethanolaminopropyl group, is substituted on the nitrogen of theβ-amino ester moiety of the compound.

The term aromatic, as used herein, refers to a moiety having delocalizedelectrons due to conjugated double bonds, which may form a ring (as inan aryl moiety); heteroaromatic means an aromatic compound in which acarbon is replaced with one or more nitrogen, oxygen, phosphorus,silicon or sulfur atoms.

In general, the terms aryl and heteroaryl, as used herein, refer tomono- or polycyclic, heterocyclic, and polyheterocyclic unsaturatedmoieties having preferably 3-14 carbon atoms, each of which may besubstituted or unsubstituted. Substituents include, but are not limitedto, any of the previously mentioned substituents, i.e., the substituentsrecited for aliphatic moieties, or for other moieties as disclosedherein, resulting in the formation of a stable compound. In certainembodiments of the present invention, aryl refers to a mono- or bicycliccarbocyclic ring system having one or two aromatic rings including, butnot limited to, phenyl, naphthyl, tetrahydronaphthyl, indanyl, indenyl,and the like. In certain embodiments of the present invention, the termheteroaryl, as used herein, refers to a cyclic aromatic radical havingfrom five to ten ring atoms of which one ring atom is selected from S,O, and N; zero, one, or two ring atoms are additional heteroatomsindependently selected from S, O, and N; and the remaining ring atomsare carbon, the radical being joined to the rest of the molecule via anyof the ring atoms, such as, for example, pyridyl, pyrazinyl,pyrimidinyl, pyrrolyl, pyrazolyl, imidazolyl, thiazolyl, oxazolyl,isooxazolyl, thiadiazolyl, oxadiazolyl, thiophenyl, furanyl, quinolinyl,isoquinolinyl, and the like.

It will be appreciated that aryl and heteroaryl groups can beunsubstituted or substituted, wherein substitution includes replacementof one, two, three, or more of the hydrogen atoms thereon independentlywith any one or more of the following moieties including, but notlimited to: aliphatic; heteroaliphatic; aryl; heteroaryl; arylalkyl;heteroarylalkyl; alkoxy; aryloxy; heteroalkoxy; heteroaryloxy;alkylthio; arylthio; heteroalkylthio; heteroarylthio; —F; —Cl; —Br; —I;—OH; —NO₂; —CN; —CF₃; —CH₂CF₃; —CHCl₂; —CH₂OH; —CH₂CH₂OH; —CH₂NH₂;—CH₂SO₂CH₃; —C(O)R_(x); —CO₂(R_(x)); —CON(R_(x))₂; —OC(O)R_(x);—OCO₂R_(x); —OCON(R_(x))₂; —N(R_(x))₂; —S(O)₂R_(x); —NR_(x)(CO)R_(x),wherein each occurrence of R_(x) independently includes, but is notlimited to, aliphatic, heteroaliphatic, aryl, heteroaryl, arylalkyl, orheteroarylalkyl, wherein any of the aliphatic, heteroaliphatic,arylalkyl, or heteroarylalkyl substituents described above and hereinmay be substituted or unsubstituted, branched or unbranched, cyclic oracyclic, and wherein any of the aryl or heteroaryl substituentsdescribed above and herein may be substituted or unsubstituted.Additional examples of generally applicable substituents are illustratedby the specific embodiments shown in the Examples that are describedherein.

The term carboxylic acid as used herein refers to a group of formula—CO₂H.

The terms halo and halogen as used herein refer to an atom selected fromfluorine, chlorine, bromine, and iodine.

The term heteroaliphatic, as used herein, refers to aliphatic moietiesthat contain one or more oxygen, sulfur, nitrogen, phosphorus, orsilicon atoms, e.g., in place of carbon atoms. Heteroaliphatic moietiesmay be branched, unbranched, cyclic or acyclic and include saturated andunsaturated heterocycles such as morpholino, pyrrolidinyl, etc. Incertain embodiments, heteroaliphatic moieties are substituted byindependent replacement of one or more of the hydrogen atoms thereonwith one or more moieties including, but not limited to aliphatic;heteroaliphatic; aryl; heteroaryl; arylalkyl; heteroarylalkyl; alkoxy;aryloxy; heteroalkoxy; heteroaryloxy; alkylthio; arylthio;heteroalkylthio; heteroarylthio; —F; —Cl; —Br; —I; —OH; —NO₂; —CN; —CF₃;—CH₂CF₃; —CHCl₂; —CH₂OH; —CH₂CH₂OH; —CH₂NH₂; —CH₂SO₂CH₃; —C(O)R_(x);—CO₂(R_(x)); —CON(R_(x))₂; —OC(O)R_(x); —OCO₂R_(x); —OCON(R_(x))₂;—N(R_(x))₂; —S(O)₂R_(x); —NR_(x)(CO)R_(x), wherein each occurrence ofR_(x) independently includes, but is not limited to, aliphatic,heteroaliphatic, aryl, heteroaryl, arylalkyl, or heteroarylalkyl,wherein any of the aliphatic, heteroaliphatic, arylalkyl, orheteroarylalkyl substituents described above and herein may besubstituted or unsubstituted, branched or unbranched, cyclic or acyclic,and wherein any of the aryl or heteroaryl substituents described aboveand herein may be substituted or unsubstituted. Additional examples ofgenerally applicable substituents are illustrated by the specificembodiments shown in the Examples that are described herein.

The term heterocyclic, as used herein, refers to an aromatic ornon-aromatic, partially unsaturated or fully saturated, 3- to10-membered ring system, which includes single rings of 3 to 8 atoms insize and bi- and tri-cyclic ring systems which may include aromaticfive- or six-membered aryl or aromatic heterocyclic groups fused to anon-aromatic ring. These heterocyclic rings include those having fromone to three heteroatoms independently selected from oxygen, sulfur, andnitrogen, in which the nitrogen and sulfur heteroatoms may optionally beoxidized and the nitrogen heteroatom may optionally be quaternized. Incertain embodiments, the term heterocylic refers to a non-aromatic 5-,6-, or 7-membered ring or a polycyclic group wherein at least one ringatom is a heteroatom selected from O, S, and N (wherein the nitrogen andsulfur heteroatoms may be optionally oxidized), including, but notlimited to, a bi- or tri-cyclic group, comprising fused six-memberedrings having between one and three heteroatoms independently selectedfrom the oxygen, sulfur, and nitrogen, wherein (i) each 5-membered ringhas 0 to 2 double bonds, each 6-membered ring has 0 to 2 double bonds,and each 7-membered ring has 0 to 3 double bonds, (ii) the nitrogen andsulfur heteroatoms may be optionally oxidized, (iii) the nitrogenheteroatom may optionally be quaternized, and (iv) any of the aboveheterocyclic rings may be fused to an aryl or heteroaryl ring.

The term aromatic heterocyclic, as used herein, refers to a cyclicaromatic radical having from five to ten ring atoms of which one ringatom is selected from sulfur, oxygen, and nitrogen; zero, one, or tworing atoms are additional heteroatoms independently selected fromsulfur, oxygen, and nitrogen; and the remaining ring atoms are carbon,the radical being joined to the rest of the molecule via any of the ringatoms, such as, for example, pyridyl, pyrazinyl, pyrimidinyl, pyrrolyl,pyrazolyl, imidazolyl, thiazolyl, oxazolyl, isooxazolyl, thiadiazolyl,oxadiazolyl, thiophenyl, furanyl, quinolinyl, isoquinolinyl, and thelike. Aromatic heterocyclic groups can be unsubstituted or substitutedwith substituents selected from the group consisting of branched andunbranched alkyl, alkenyl, alkynyl, haloalkyl, alkoxy, thioalkoxy,amino, alkylamino, dialkylamino, trialkylamino, acylamino, cyano,hydroxy, halo, mercapto, nitro, carboxyaldehyde, carboxy,alkoxycarbonyl, and carboxamide.

The term carbonyldioxyl, as used herein, refers to a carbonate group ofthe formula —O—CO—OR.

The term carbamoyl, as used herein, refers to an amide group of theformula —CONH₂.

The term hydrocarbon, as used herein, refers to any chemical groupcomprising hydrogen and carbon. The hydrocarbon may be substituted orunsubstitued. The hydrocarbon may be unsaturated, saturated, branched,unbranched, cyclic, polycyclic, or heterocyclic. Illustrativehydrocarbons include, for example, methyl, ethyl, n-propyl, iso-propyl,cyclopropyl, allyl, vinyl, n-butyl, tert-butyl, ethynyl, cyclohexyl,methoxy, diethylamino, and the like. As would be known to one skilled inthis art, all valencies must be satisfied in making any substitutions.

The term thiohydroxyl or thiol, as used herein, refers to a group of theformula —SH.

The term ureido, as used herein, refers to a group of the formula—NH—CO—NH₂

The following are more general terms used throughout the presentapplication:

As used herein, the singular forms “a”, “an”, and “the” include theplural reference unless the context clearly indicates otherwise. Thus,for example, a reference to “a monomer” includes a plurality of suchmonomers.

The term “keratin” as used herein refers any one of a class of fibrousstructural proteins found in hair, wool, and nails. Keratin proteinscontains a large quantity of cysteine residues. Human hair is a keratinthat has approximately 15% cysteine residues cross-linked by disulfidebridges.

As used herein, a “monomer” is a repeating structural unit appearing ina polymer or an oligomer. Thus, for example, the polymer polybutadieneis comprised of repeating units derived from butadiene.

The term “oligomer,” as used herein, refers to a chemical compound withless than 10 repeating structural units. In particular, a compoundaccording to the invention containing less than 10 β-amino ester groupsis considered an oligomer, notwithstanding the size of the blockconnecting the amino ester groups.

The term “polymer,” as used herein, refers to a chemical compound ofrepeating structural units (monomers) connected by covalent bonds. Apolymer is typically of high molecular weight comprising 10 s to 100 sto 1000 s or even more monomers. However, as used herein, the term“polymer” also includes “oligomers.”

The term “rubber,” as used herein, means a compound containing repeatingunits of butadiene, isoprene, chloroprene, styrene-butadiene, orvariations thereof, and also includes ethylene vinyl acetate (EVA) (suchas sold under the tradename Elvax®), urethane rubber, silicone rubber orsilicone elastomer. These units incorporated in a molecule constitutethe “rubber moiety” of the molecule, as that term is used herein.

The symbol

in a chemical structure means that different atoms and/or bonds may befound at that position. Thus, in formula (I), A is designated withsymbol

because a number of options exist for the configuration of A. Inconnection with the end groups, to form an acrylate or methacrylate endgroup, for example, Z

means that Z and the carbon to which it is attached form a CH₂═ terminusof the acrylate or methacrylate end group. Alternatively, in the sameformula, the

symbol may represent a bond with the next monomer repeat group.

Preferred Embodiments

Hair treatment compositions according to the invention comprise aβ-amino ester compound which may be formed by reacting a diacrylate ordimethacrylate with an amine according to one of the following generalreaction schemes:

In these formulas R₁ is a hydrogen or methyl, which defines the startingmaterial as a diacrylate or a dimethacrylate. R₂, R₃, and R₄ areselected from the group consisting of alkyl, alkenyl, alkynyl, acyl,alkoxy, alkoxyalkyl, amino, aminoalkyl, aryl, heteroaryl, amido,alkylthioether, carbamoyl, carbonyldioxyl, carboxyl ester, cyclicaliphatic, cyclic heteroaliphatic, aromatic, heteroaromatic and ureidogroups, each of which groups may be substituted with at least onesubstituent selected from the group consisting of alkyl, alkenyl,alkynyl, acyl, alkoxy, alkoxylalkyl, amino, aminoalkyl, aryl,heteroaryl, amido, cyclic aliphatic, heterocyclic aliphatic, halogen,hydroxyl, cyano, carbamoyl, carboxylic acid, carbonyldioxyl,alkylthioether, siloxyl, and thiohydroxyl groups.

If the starting material is a dimethacrylate, the above reactions formcompounds represented by the corresponding formulas (I′) and (II″),wherein A, B, Z, Z′ and n are as defined above for formulas (I) and(II):

Where the starting material is a diacrylate, the above reactions formcompounds represented by the corresponding formulas (I) and (II):

Such compounds include, without limitation, the compounds disclosed inthe aforementioned patents and published applications incorporated byreference.

In an embodiment of the present invention, n is in the range of 1 to10,000. In certain other embodiments of the present invention, n is inthe range of 1 to 1,000, 1 to 100 or 3 to 10.

In preferred embodiments, the acrylate or methacrylate moieties in thecompounds are linked by a relatively high molecular weight moiety A. Inthe presently preferred embodiments, A is a rubber moiety, includingwithout limitation, a material comprising monomers selected frombutadiene, styrene-butadiene, chloroprene, and isoprene monomers.

Rubber-containing materials that may be reacted to form a polymeraccording to the invention include, without limitation, polybutadienediacrylate, which is represented by the formula

or its corresponding dimethacrylate.

Polyisoprene diacrylate may also be used, represented by the followingformula,

The corresponding dimethacrylate may also be used.

In these starting materials m may be 1 to 60, and in certain embodiments1 to 40, 1 to 30 or 20 to 30.

Alternatively, polychloroprene or styrene-butadiene rubbers may bemodified into diacrylates or dimethacrylates, which can then be reactedaccording to the general reaction schemes I and II above.Styrene/butadiene rubbers have the following general structure:

Poly-chloroprene has the general structure

In presently preferred embodiments polybutadiene diacrylates (PBDs) areemployed as a starting material. Although not limiting the invention,diacrylates and dimethacrylates having a number average molecular weightin the range of 1000 g/mol to 5,000 g/mol may be used. In the exampleselaborated below, two different starting material were used, having anumber average molecular weight of 1400 g/mol and 3000 g/mol,respectively.

In other embodiments, A is an optionally substituted carbon chain orheteroatom containing carbon chain containing 1 to 30 atoms in thechain. Thus, in some instances, 1,4-butanediol diacrylate,1,4-butanediol dimethacrylate, 1,2-ethanediol diacrylate, 1,6-hexanedioldiacrylate, 2,5-hexanediol diacrylate, and 1,3-propanediol diacrylatemay be used as a diacrylate starting material, such that A comprises acarbon chain having less than 30 atoms.

The linker A between the acrylate or methacrylate moieties of thecompound may comprise a substituted carbon chain wherein thesubstituents join to form one or more rings. For example, suchmulticyclic moiety A may be represented by the formula

The corresponding compound useful in a hair treatment compositionaccording to the invention has the following formula, wherein Z, Z′ andR₂ are as described above.:

Alternatively, linker A may comprise a carbon chain orheteroatom-containing carbon chain having one or more aromaticsubstituents on the chain, resulting in compounds according to thefollowing formula,

The diacrylate or dimethacrylate starting material may be reacted withamines having varying functional groups at varying ratios. For example,acceptable PBD:amine ratios may range from about 1:2 to about 2:1. Inthe examples elaborated below, PBD:amine ratios were varied between1:1.8 and 1:1.2.

The compounds according to the invention, resulting from theabove-described reaction, sometimes have small amounts of unreactedamine. In preferred embodiments, the compound used in the compositionaccording to the invention contains less than 1 wt %, preferably lessthan 0.1 wt %, and more preferably less than 0.01 wt % unreacted amine.

A suitable diacrylate or dimethacrylate may be reacted with a primaryamine having a formula NH₂R₂ (where R₂ is as defined above) by MichaelAddition. The R₂ group on the primary amine may be selected to impartdesired properties to the composition. Thus, the amine may be selectedto modify the properties imparted to the composition by the rubbermoiety, to reduce a greasy, heavy feel while maintaining the frictionalattributes obtained with the rubber, for example. Alternatively,hydrophilic groups may be incorporated into the compound via the amineto improve water solubility. Likewise, hydrophobic groups may be used toimprove oil phase formulation and/or interaction with hair lipids.Aromatic moieties and styrene-containing moieties may be used toincrease the stiffness of the finished compounds.

The following primary amines have been used to formulate compoundsaccording to the invention: propylamine; butylamine; pentylamine;hexylamine; octylamine; 1-aminodecane; isopropylamine; sec-butylamine;isobutylamine; tert-butylamine; 2-aminopentane; isopentylamine;2-amino-6-methylheptane; 3-(dimethylamino)-1-propylamine;2-diethylaminoethylamine; 2-(diisopropylamino)ethylamine;3-(diethylamino)propylamine; N,N-dimethylethylenediamine; ethanolamine;3-amino-1-propanol; amino-2-propanol; 4-amino-1-butanol;5-amino-1-pentanol; 6-amino-1-hexanol; n-(3-aminopropyl)diethanolamine;2-(2-aminoethoxy)ethanol; 2-methoxyethylamine; 3-methoxypropylamine;3-ethoxypropylamine; 3-butoxypropylamine; aminoacetaldehyde dimethylacetal; 3-Isopropoxypropylamine; aminoacetaldehyde diethyl acetal;4-aminobutyraldehyde diethyl acetal; 3-aminopropyltriethoxysilane;2-methoxybenzylamine; 4-methoxybenzylamine; 2-phenoxyethylamine;3,4-dimethoxyphenethylamine; 4-methoxyphenethylamine;2-methoxyphenethylamine; tyramine; benzylamine; 4-methylbenzylamine;phenethylamine; 4-aminobenzylamine; 4-tert-butylbenzylamine;4-phenylbenzylamine; 4-iodobenzylamine; 4-(aminomethyl)pyridine;3-picolylamine; 2-fluorobenzylamine; 4-fluorobenzylamine;4-fluorophenethylamine; 3-(trifluoromethyl)benzylamine;2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9-heptadecafluorononylamine;cyclopropylamine; cyclopentylamine; N-(3-aminopropyl)-2-pyrrolidinone;cyclohexylamine; cyclohexanemethylamine; 2-(1-cyclohexenyl)ethylamine;1-(2-aminoethyl)piperidine; 3-morpholinopropylamine;(±)-3-amino-1,2-propanediol; 2-amino-1,3-propanediol;2-Amino-2-methyl-1,3-propanediol; 2-amino-2-ethyl-1,3-propanediol;N,N-bis(2-hydroxyethyl)ethylenediamine; oxamic Acid; and2-amino-2-(hydroxymethyl)propane-1,3-diol.

Suitable amines containing siloxyl substituents may be used as startingmaterials, including, without limitation,3-aminopropyl(diethoxy)methylsilane; 3-(2-aminoethylamino)propyldimethoxymethylsilane;N-[3-(trimethoxysilyl)propyl]ethylenediamine;3-[2-(2-aminoethylamino)ethylamino]propyl-trimethoxysilane; and1-[3-(trimethoxysilyl)propyl]urea.

The amino acids, including Alanine, Leucine, Serine, Cysteine, Tyrosine,Glutamic Acid, Glutamine, Lysine, and Arginine are also suitable to formcompounds according to the invention.

Alternatively, a bis (amine) starting material may be used. The aminegroups in such bis (amine) starting materials are linked by a moiety B,as shown in reaction scheme II above. In general B is a carbon chain ora heteroatom-containing carbon chain, optionally substituted with atleast one substituent selected from the group consisting of alkyl,alkenyl, alkynyl, amino, alkylamino, dialkylamino, trialkylamino,aminoalkyl aryl, ureido, heterocyclic, aromatic heterocyclic, cyclic,aromatic cyclic, halogen, hydroxyl, alkoxy, cyano, amido, carbamoyl,carboxylic acid, ester, carbonyl, carbonyldioxyl, alkylthioether, andthiol groups.

Bis(secondary amine) monomers that are useful in the present inventioninclude, but are not limited to, N,N′-dimethylethylenediamine,piperazine, 2-methylpiperazine, 1,2-bis(N-ethylamino)ethylene, and4,4′-trimethylenedipiperidine.

End groups Z and Z′, together with the atoms to which they are attached,represent acrylate, methacrylate or amino end group. In embodiments, Zand Z′ form an amino group or unsaturated acrylate or methacrylate groupon both termini of the polymer. Thus, for example, in the case where Zand Z′ form an amino moiety, Z′ is hydrogen and Z is —NR₂—H. Where theend group is acrylate, Z

means that Z and the carbon to which it is attached form a CH₂ 50terminus of the acrylate or methacrylate end group while Z′ forms anacrylate or methacrylate group.

Non-limiting examples of polymers with amine terminated end groups andacrylate terminated end groups are:

wherein y is 1 to 100.

In embodiments, n in formulas (I) to (IV) may range from 1 to 10,000.However, presently preferred compounds of the invention are oligomers,having 3 to 10 amino ester units. A composition according to theinvention may contain a plurality of oligomers of different length.

The preferred compositions used in the invention include a cosmeticallyacceptable carrier such that the composition can be applied to the hairwithout irritation to the eyes or scalp. The compositions may be in theform of an oil-in-water emulsion, a water-in-oil emulsion, a dispersion,a suspension, a cream, a foam, a gel, a spray, a powder, a liquid or apomade.

The β-amino ester compound is generally present in the composition in arange of about 0.01 percent by weight to about 20 percent by weight ofthe composition. In embodiments, the β-amino ester is present in a rangeof about 0.1 percent by weight to about 10.0 percent by weight of thecomposition; and in still other embodiments in a range of about 1.0percent by weight to about 5.0 percent by weight.

The compositions according to the invention are preferably water orwater-alcohol based, meaning that that they contain greater than 50percent by weight water. Preferably water is present in the compositionsaccording to the invention in a range of 60 to 99 percent by weight ofthe composition. In the presently preferred embodiments, water ispresent in a range of about 80 to about 95 percent by weight of thecomposition.

The cosmetically acceptable carrier for the compound containsingredients conventionally used in hair treatment compositions. One ormore emulsifiers may be included in a range of about 0.1 to about 10.0percent by weight, in preferred embodiments, in a range of about 0.5percent by weight to about 3.0 percent by weight. Suitable formulationamounts may be determined by those of ordinary skill in the art withoutundue experimentation, depending on how the composition is intended tobe delivered. Suitable emulsifiers may be selected from those known inthe art, including without limitation, Polysorbate 20, Polyacrylate-13,Polyisobutene, Oleth-10, and the like.

A fatty alcohol, or a mixture, may be provided in an amount of 0.1 toabout 5.0 percent by weight of the composition to provide thickeningand/or emollient properties. In embodiments, a fatty alcohol componentsuch as cetearyl alcohol (a mixture of fatty alcohols), may be providedin a range of about 0.1 to 1.0 percent by weight of the composition.

One or more fatty acids may be provided in a range of about 0.1 percentby weight to 5.0 percent by weight of the composition. Fatty acids,include without limitation, palmitic acid, stearic acid, linoleic acid,myristic acid, and others known in the art to provide thickening and/oremollient properties in a hair treatment composition.

Compositions according to the invention may also include at least oneadditive conventionally used in hair treatment compositions.Non-limiting examples of suitable additives include emollients,processing aids, dyes, anionic surfactants, cationic surfactants,nonionic surfactants, amphoteric surfactants, fragrances, screeningagents, preserving agents, proteins, vitamins, silicones, polymers suchas thickening polymers, plant oils, mineral oils, synthetic oils and anyother additive conventionally used in compositions for the care and/ortreatment of keratinous fibers.

General Synthetic Procedure

The synthesis of the compounds described below was performed in 30 mlclear glass jars with phenolic caps lined with polyethylene core liners,and stirred with 15.9×9.5 mm Teflon® coated spin bar. For each reaction,5 g of PBD was added to each vial Amine was added by pipette for liquidsor by mass for solids at desired ratios. Vials were stirred at 90° C.for 48 hours. The spin bar was removed while the reaction material wasstill hot. Polymers were allowed to cool to room temperature beforeobserving for color and viscosity as a rough monitor of reactioncompleteness. As the reactions went to completion, the viscositydramatically increased and the mixtures turned more yellow/amber incolor. Products were stored at 4° C.

Primary amines were obtained from Sigma-Aldrich, Inc. (St. Louis, Mo.)and VWR International, LCC (West Chester, Pa.). PBDs were obtained fromSartomer Company, Inc. (Exton, Pa.) (Sartomer product #CN307) and SanEsters (New York, N.Y.) (product # BAC-15 and BAC-45).

Example 1-1

The above polymer was synthesized following the procedure outlined aboveusing 5.0 grams of polybutadiene diacrylate (99%) having a molecularweight of 3000 Da (1 equivalent) and 325.11 mg of N-(3-aminopropyl)diethanolamine (1.2 equivalents). The resulting material wascharacterized via ¹H NMR.

HNMR (CDCl₃): δ (ppm) 1.0-1.3 (m), 1.3-1.5 (m), 1.6-1.7 (m), 1.8-2.2(m), 2.4-2.5 (m), 2.5-2.7 (m), 2.7-2.8 (m), 3.6-3.7 (m), 4.8-5.1 (m),5.2-5.4 (m), 5.4-5.7 (m).

All NMR spectra were recorded on a Varian Mercury 300 MHz spectrometerand taken in CDCl3.

In like manner, Examples 1-2 through 1-11 below were formed frompolybutadiene diacrylate polymer (molecular weight 1400 Da or 3000 Da)and suitable amines to form the β-amino ester compounds listed below.Compositions were formulated and tested as set forth below.

Example 1-2

Example 1-3

Example 1-4

Example 1-5

Example 1-6

Example 1-7

Example 1-8

Example 1-9

Example 1-10

Example 1-11

Example 2-1 Feel Test

The feel properties of preferred polymers on hair were assessed. 10 g ofa 1% (w/w) in THF solution was prepared. Solutions were applied to dry 1g×2.5 cm wide×22 cm long hair tresses of virgin straight medium brownhair (International Hair Importers). Tresses were curled with a ½ in.diameter curling iron (Hot Tools Model 1101) on the highest heat setting(approximately 200° C.) for 30 seconds. Each tress was evaluated withclean hands for the following attributes: tack, grease, friction, andthe presence of a coating. Each attribute was rated against thefollowing scale: 0=none, 1=slight, 2=moderate, 3=excessive.

The desired feel properties are no grease, no tackiness, very littlecoating or none at all, and slight friction. The results obtained inTable 1 were exemplary of preferred compositions, based on the feelproperties obtained.

TABLE 1 Compound Tack Grease Coating Friction PBD:amine 1:1.214PBD:octylamine 0 0 1 0 14PBD:amino 2-propanol 0 0 1 014PBD:n-(3-aminopropyl) 0 0 0 2 diethanolamine14PBD:4-methoxybenzylamine 0 0 1 0 14PBD:4-(Aminomethyl)pyridine 0 0 1 030PBD:3-amino-1-propanol 0 0 1 0 30PBD:4-amino-1-butanol 1 0 0 030PBD:2-(2-Aminoethoxy)ethanol 1 0 0 0 PBD:amine 1:1.814PBD:3-aminopropyltriethoxysilane 0 0 2 0 14PBD:4-Methoxybenzylamine 10 1 0 14PBD:4-(Aminomethyl)pyridine 0 0 1 0 30PBD:ethanolamine 1 0 0 030PBD:n-(3-aminopropyl) 0 0 0 1 diethanolamine 14PBD means polybutadienediacrylate having a molecular weight of 1400 Da. 30PBD meanspolybutadiene diacrylate having a molecular weight of 3000 Da.

Example 3-1 Snap and Movement Test

The movement of hair treated with each polymer in Table 1 was assessed.A 1% (w/w) solution of 10 g of each polymer in THF was prepared.Solutions were applied to dry 1 g×2.5 cm wide×22 cm long hair tresses ofvirgin straight medium brown hair (International Hair Importers).Tresses were curled with a ½ inch diameter curling iron (Hot Tools Model1101) on the highest heat setting (approximately 200° C.) for 30seconds. Once cool, the ends of the tress were extended to full lengthand released. Snap is defined as the initial recoil of the tress, whilemovement is defined as the length of time after the initial recoil thatthe tress was in motion, as well as the intensity of motion. Bothattributes were rated against the following scale: 0=poor, 1=ok, 2=good,3=great, 4=excellent. Scores of 4 for both snap and movement weredesired.

The results for snap and movement for thirteen compounds tested aregiven in Table 2.

TABLE 2 Compound Snap Movement PBD:amine (1:1.2) 14PBD:octylamine 3 314PBD:amino 2-propanol 2 2 14PBD:n-(3-aminopropyl) 3 3 diethanolamine14PBD:4-methoxybenzylamine 3 3 14PBD:4-methoxybenzylamine 3 330PBD:4-(Aminomethyl)pyridine 2 2 30PBD:3-amino-1-propanol 0 030PBD:4-amino-1-butanol 2 2 PBD:amine 1:1.814PBD:3-aminopropyltriethoxysilane 3 3 14PBD:4-Methoxybenzylamine 3 314PBD:4-(Aminomethyl)pyridine 3 3 30PBD:Ethanolamine 3 330PBD:n-(3-aminopropyl) 2 2 diethanolamine

The polymers on Table 3 were chosen as exhibiting better propertiesbased on the overall results obtained in the feel and the snap/movementtests. Feel scores were given more weight than snap/movement scores asfeel is a more desirable property.

TABLE 3 Coat- Move- Compound Tack Grease ing Friction Snap ment PBD:amine1: 1.2 14PBD: octylamine 0 0 1 0 3 3 14PBD: amino 2- 0 0 1 0 2 2propanol 14PBD: n-(3- 0 0 0 2 3 3 aminopropyl) diethanolamine 14PBD: 4-0 0 1 0 3 3 methoxybenzylamine 14PBD: 4- 0 0 1 0 3 3 methoxybenzylamine

Example 4-1 Consumer Use Test

β-amino ester compound according to Example 1-1 was formulated into acream according to Formulation Example 5-1 below and a cream accordingto Formulation Example 5-2. These two formulations were given to 20women. The women in the study were blinded to the ingredients and thepotential performance benefits of the formulations. The women were askedto use each product for one week. Typically, the formulations wereapplied to wet hair and blown dry to a desired style. After using thetwo formulations, the women were interviewed and asked to fill out aproduct performance survey. The needs of the 20 women compared to howthe two formulations delivered against those needs are shown in Table 4.

TABLE 4 Benefit Benefit Delivered Delivered Desired Benefit PriorityFrom Cream From Spray Volume and body High High Med Thickening High HighMed Weightlessness High High Med Lasting Effect High High Low Ease ofAchieving High Med Low Effect Lack of Residue Med Med Low Softness LowMed Low Shine/Conditioning Med Med Low Smoothness Med Med LowHold/Control/Texture Med Med Low Ease of Use Med Med High Pleasant SmellMed Low Low

Formulation Example 5-1

A styling cream containing β-amino ester compound according to theinvention may include the following:

Ingredients % w/w Water q.s. β-amino ester compound 0.50-6.00Polysorbate 20 (and) Polyacrylate-13 (and) Polyisobutene 0.50-4.00(Emulsifier) Fragrance 0.20-3.00 Phenoxyethanol (and)Methylisothiazolinone (Preservative) 0.50-1.50 PPG-2 Myristyl EtherPropionate (Emollient) 0.10-5.00 Oleth-10 (Emulsifier) 0.10-2.00

Formulation Example 5-2

A styling cream containing β-amino ester compound was prepared with thefollowing ingredients:

Ingredients % w/w Water 93.00 β-amino ester compound 3.00 Polysorbate 20(and) Polyacrylate-13 (and) Polyisobutene 1.45 Fragrance 1.00Phenoxyethanol (and) Methylisothiazolinone 0.50 PPG-2 Myristyl EtherPropionate 0.50 Oleth-10 0.50

The above composition was manufactured using the process describedbelow.

A vessel was charged with water (Phase A) and heated to 75 ° C. Phase Bconsisting of polysorbate 20, polyacrylate-13, and polyisobutene wasadded to Phase A using high agitation and allowed to mix for 30 minutesor until homogeneous. The 3-amino ester compound, oleth-10, and PPG-2myristyl ether propionate were mixed in a separate vessel at 75 ° C.until homogeneous to form Phase C. Phase C was added to the abovemixture of Phase A and Phase B and the contents were mixed untilhomogeneous. The mixture was cooled to 40 ° C. Thereafter, Phase D,consisting of phenoxyethanol, and methylisothiazolinone, was added tothe above mixture and the contents were mixed until homogeneous. Themixture was cooled to 30° C. Phase E, consisting of fragrance, was addedto the above mixture and the contents were mixed until homogeneous.Water (q.s.) was added to the mixture and homogenized to obtain theabove composition.

Formulation Example 5-3

A styling spray containing β-amino ester compound according to theinvention may include the following:

Ingredients % w/w Water q.s. β-amino ester compound 0.50-6.00 Oleth-10(Emulsifier)  0.10-10.00 Ethoxydiglycol Oleate (Emollient) 0.10-5.00Fragrance 0.20-3.00 Phenoxyethanol (and) Methylisothiazolinone(Preservative) 0.50-1.50 Sodium Chloride 0.10-1.50 Xanthan Gum (Rheologymodifier) 0.10-1.50

Formulation Example 5-4

A styling spray containing β-amino ester compound was prepared with thefollowing ingredients:

Ingredients % w/w Water 92.70 β-amino ester compound 3.00 Oleth-10 1.10Ethoxydiglycol Oleate 1.00 Fragrance 1.00 Phenoxyethanol (and)Methylisothiazolinone 0.50 Sodium Chloride 0.40 Xanthan Gum 0.30

The above composition may be manufactured using the process describedbelow.

A vessel was charged with water and xanthan gum was added to form PhaseA. Xanthan gum was allowed to hydrate for 20 minutes. Phase A was thenheated to 75° C. In a separate vessel, the β-amino ester compound,oleth-10 and ethoxydiglycol oleate were heated to 75° C. and mixed toform a homogeneous Phase B. Phase B was added to Phase A and mixed untilhomogeneous. The mixture was cooled to 40° C. Thereafter, Phase C,consisting of phenoxyethanol and methylisothiazolinone, was added to theabove mixture and the contents mixed until homogeneous. The mixture wascooled to 30° C. Then, Phase D consisting of sodium chloride andfragrance was added to the above mixture and the contents were mixeduntil homogeneous. Water (q.s.) was added to the mixture and homogenizedto obtain the above composition.

Formulation Example 5-5

A styling non-aerosol mousse containing β-amino ester compound accordingto the invention may include the following:

Ingredients % w/w Water q.s. β-amino ester compound 0.50-6.00Cocamidopropylamine Oxide (Surfactant)  0.10-10.00 Oleth-10 (Emulsifier) 0.10-10.00 Ethoxydiglycol Oleate (Emollient) 0.10-5.00 Fragrance0.20-3.00 Phenoxyethanol (and) Methylisothiazolinone (Preservative)0.50-1.50 Sodium Chloride 0.10-1.50 Xanthan Gum (Rheology modifier)0.10-1.50

Formulation Example 5-6

A styling non-aerosol mousse containing β-amino ester compound wasprepared with the following ingredients:

Ingredients % w/w Water 89.70 β-amino ester compound 3.00Cocamidopropylamine Oxide 3.00 Oleth-10 1.10 Ethoxydiglycol Oleate 1.00Fragrance 1.00 Phenoxyethanol (and) Methylisothiazolinone 0.50 SodiumChloride 0.40 Xanthan Gum 0.30

The above composition was manufactured using the process describedbelow.

To form Phase A, a vessel was charged with water and xanthan gum.Xanthan gum was allowed to hydrate for 20 minutes. Phase A was thenheated to 75° C. To obtain Phase B, β-amino ester compound, oleth-10 andethoxydiglycol oleate were heated to 75° C. in a separate vessel. Thecontents were mixed until homogeneous. Phase B was added to Phase A andmixed until homogeneous. The mixture was cooled to 40° C. Thereafter,Phase C, consisting of phenoxyethanol and methylisothiazolinone, wasadded to the above mixture and the contents were mixed untilhomogeneous. The mixture was cooled to 30° C. Thereafter, Phase D,consisting of Cocamidopropylamine oxide, sodium chloride and fragrancewas added to the above mixture of Phases A, B, and C until a homogeneouscomposition above was obtained. Water (q.s.) was added to the mixtureand mixed until homogeneous.

Notwithstanding anything herein to the contrary, the foregoingembodiments are exemplary only and not to be considered as limiting theinvention, which is defined by the appended claims.

1. A compound according to formula (I):

wherein n is an integer between 1 and 10,000; Z and Z′, together withthe atoms to which they are attached, represent acrylate, methacrylateor amino end groups; R₂ is selected from the group consisting of alkyl,alkenyl, alkynyl, acyl, alkoxy, alkoxyalkyl, amino, aminoalkyl, aryl,heteroaryl, amido, alkylthioether, carbamoyl, carbonyldioxyl, carboxylester, cyclic aliphatic, cyclic heteroaliphatic, aromatic,heteroaromatic and ureido groups, each of which groups may besubstituted with at least one substituent selected from the groupconsisting of alkyl, alkenyl, alkynyl, acyl, alkoxy, alkoxylalkyl,amino, aminoalkyl, aryl, heteroaryl, amido, cyclic aliphatic,heterocyclic aliphatic, halogen, hydroxyl, cyano, carbamoyl, carboxylicacid, carbonyldioxyl, alkylthioether, siloxyl, and thiohydroxyl groups;and A is a rubber moiety with a molecular weight in a range of about1000 g/mol to about 10,000 g/mol selected from the group consisting ofbutadiene, chloroprene, isoprene, and styrene-butadiene units.
 2. Thecompound according to claim 1, wherein A consists of butadiene units. 3.The compound according to claim 2, wherein R₂ is selected from the groupconsisting of alkyl, acyl, amino, aminoalkyl, alkoxy, alkoxyalkyl,amido, each of which groups may be substituted with at least onesubstituent selected from the group consisting of alkoxy, alkoxylalkyl,amino, aminoalkyl, heteroaryl, amido, halogen, hydroxyl, cyano,carbamoyl, carboxylic acid, carbonyldioxyl, alkylthioether, siloxyl, andthiohydroxyl groups.
 4. The compound according to claim 3, wherein R₂ isalkyl or aminoalkyl group substituted with at least one substituentselected from the group consisting of alkoxy, alkoxylalkyl, amino,aminoalkyl, heteroaryl, amido, halogen, hydroxyl, cyano, carbamoyl,carboxylic acid, carbonyldioxyl, alkylthioether, siloxyl, andthiohydroxyl groups.
 5. The compound according to claim 3, wherein R₂ ishydroxyl substituted aminoalkyl.
 6. The compound according to claim 2,wherein n is 1 to
 100. 7. A compound according to formula (II):

wherein n is an integer between 1 and 10,000; Z and Z′, together withthe atoms to which they are attached, represent acrylate methacrylate oran amino end groups; R₃ and R₄ are independently selected from the groupconsisting of alkyl, alkenyl, alkynyl, acyl, alkoxy, alkoxyalkyl, amino,aminoalkyl, aryl, heteroaryl, amido, alkylthioether, carbamoyl,carbonyldioxyl, carboxyl ester, cyclic aliphatic, cyclicheteroaliphatic, aromatic, heteroaromatic and ureido groups, each ofwhich groups may be substituted with at least one substituent selectedfrom the group consisting of alkyl, alkenyl, alkynyl, acyl, alkoxy,alkoxylalkyl, amino, aminoalkyl, aryl, heteroaryl, amido, cyclicaliphatic, heterocyclic aliphatic, halogen, hydroxyl, cyano, carbamoyl,carboxylic acid, carbonyldioxyl, alkylthioether, siloxyl, andthiohydroxyl groups; B is a chain of 1 to 30 carbon atoms or heteroatomswhich atoms or heteroatoms are unsaturated, saturated with hydrogen, orare substituted with at least one substituent selected from the groupconsisting of alkyl, alkenyl, alkynyl, aryl, heteroaryl, alkoxy,alkoxyalkyl carbamoyl, carboxyl ester, carbonyldioxyl, amido,thiohydroxyl, alkylthioether, cyano, ureido, cyclic aliphatic, aromatic,and heteroaromatic groups, which substituents may be substituted orunsubstituted, or alternatively may bond with each other or with an atomon the chain to form a ring; and A is a rubber moiety with a molecularweight in a range of about 1000 g/mol to about 10,000 g/mol selectedfrom the group consisting of butadiene, chloroprene, isoprene, andstyrene-butadiene units.
 8. The compound according to claim 7, wherein Aconsists of butadiene units.
 9. The compound according to claim 8,wherein R₃ and R₄ are independently selected from the group consistingof alkyl, acyl, amino, aminoalkyl, alkoxy, alkoxyalkyl, amido, each ofwhich groups may be substituted with at least one substituent selectedfrom the group consisting of alkoxy, alkoxylalkyl, amino, aminoalkyl,heteroaryl, amido, halogen, hydroxyl, cyano, carbamoyl, carboxylic acid,carbonyldioxyl, alkylthioether, siloxyl, and thiohydroxyl groups. 10.The compound according to claim 9, wherein R₃ and R₄ are independentlyalkyl or aminoalkyl group substituted with at least one substituentselected from the group consisting of alkoxy, alkoxylalkyl, amino,aminoalkyl, heteroaryl, amido, halogen, hydroxyl, cyano, carbamoyl,carboxylic acid, carbonyldioxyl, alkylthioether, siloxyl, andthiohydroxyl groups.
 11. The compound according to claim 9, wherein R₃and R₄ are independently hydroxyl substituted aminoalkyl.
 12. Thecompound according to claim 8, wherein n is 1 to
 100. 13. The compoundaccording to claim 1, wherein the compound has the structure selectedfrom the group consisting of:

wherein y is an integer from 1 to 100; n is 1 to 100; and Z and Z′,together with the atoms to which they are attached, form an acrylate,methacrylate, or amino end group.
 14. A compound having the structure:

wherein y is an integer from 1 to 100; n is 1 to 100; and Z and Z′,together with the atoms to which they are attached, form an acrylate,methacrylate, or amino end group.
 15. A hair treatment compositioncomprising a compound according to claim 1 or 7 and a cosmeticallyacceptable carrier.
 16. The hair treatment composition of claim 15,wherein the composition is a hair styling product, shampoo, orconditioner.
 17. The hair treatment composition of claim 16 wherein thehair styling product is a spray, cream, gel, mousse, or pomade.
 18. Amethod of treating scalp hair comprising applying to the hair thecomposition according to claim 15.